JPH01254603A - Antifouling agent for fishing net - Google Patents

Abstract

PURPOSE:To obtain an antifouling agent for fishing net, having controlled initial rate of release of an aquatic life controlling component and capable of maintaining the effect to prevent the adhesion of aquatic life to an aquatic material such as a fixed shore net over a long period, by using an aquatic life controlling component, a specific resin component and a specific amount of a water-repellent component as essential components. CONSTITUTION:The objecting agent contains (A) an aquatic life controlling component having low toxicity, giving little influence to human body and fish and exhibiting high activity against aquatic life [e.g., 2-(thiocyanomethylthio) benzothiazole or tetraalkylthiuram disulfide], (B) a resin component composed of (i) a hydrophilic resin such as a mixture of acrylic resins having low molecular weight and high molecular weight and (ii) a resin compatible with the hydrophilic resin and (C) 0.5-10wt.% (based on whole solid component) of a water-repellent component such as paraffins, silicones or fluorine-based water- repellents. The amounts of the components A, B and C are 20-70wt.%, 30-80wt.% and 0.5-10wt.% based on the whole solid component, respectively. The agent is used in a state coated to or impregnated in the aquatic material.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a fish net antifouling agent, and more specifically, to a fish net antifouling agent.
The present invention relates to a fish net antifouling agent with controlled release rate, particularly initial release rate, of biological control components.

The fish net antifouling agent of the present invention is applied to underwater materials for the purpose of preventing aquatic organisms from adhering to them, such as fixed nets, aquaculture nets, and their supporting lobes that are immersed in water for a long period of time. It is used after being coated or impregnated in advance.

[Conventional technology]

Organic tin compounds such as tributyltin (TBT○), metals such as alkylated mercury, and oxidized water roots are used to prevent aquatic organisms such as algae, barnacles, serpura, and bryozoans from adhering to underwater materials such as fishing nets. Fish net antifouling agents containing compounds as aquatic organism control ingredients are known (Special Publication No. 46-01339).
2 Publication, Special Publication No. 52-3819, Special Publication No. 53-
6661, etc.) and has been widely used.

Fish net antifouling agents containing tetraalkylthiuram disulfides as aquatic organism control components are also known (see Japanese Patent Publication No. 35-5368, Japanese Patent Publication No. 39-021104, etc.).

The present inventors also found that the present invention contains at least one kind of sulfur-containing organic compounds such as para-toluenesulfonamide and 2-(thiocyanomethylthio)benzothiazole, and tetraalkylthiuram disulfinde as an aquatic organism control component, and contains metal compounds. We have proposed a fishnet prevention agent containing T3 (Japanese Patent Application Laid-Open No. 60-038306).

[Problem that the invention seeks to solve]

Aquatic materials such as fixed nets and aquaculture nets that are placed in water for long periods of time become attached to the above-mentioned aquatic organisms in a relatively short period of time, and not only do they clog the nets, but they must be removed underwater. Damage materials. In particular, blockages in aquaculture nets impede water circulation and replacement, resulting in poor growth of farmed fish due to lack of oxygen and bacterial growth! This causes the outbreak of diseases caused by aquaculture, causing great damage to aquaculture fisheries.

Fishnet repellents are used to prevent aquatic organisms from adhering to these underwater materials. The metal compound, especially TB
Fish net antifouling agents containing TO as an active ingredient are widely used because they have an extremely excellent effect of preventing aquatic organisms from adhering to underwater materials. Not only do they require special care when handling them, but their accumulation in fish bodies causes malformations and environmental pollution, which have become social problems.

Tetraalkylthiuram disulfides exhibit excellent effects in preventing aquatic organisms from adhering to fish nets, etc. when used in combination with the above metal compounds, but when used alone as an aquatic organism control ingredient, they do not prevent fish nets, etc. The effect of preventing aquatic organisms from adhering to the water is insufficient.

Therefore, when used in combination with a metal compound, it has the same problems as described above.

On the other hand, although the fish net antifouling agent proposed by the present inventors exhibits an excellent effect of preventing the adhesion of aquatic organisms, the initial %J4 elution rate of the aquatic organism control component is high, and the effect is There were times when I received

The present invention aims to provide a fish net antifouling agent that has a reduced initial elution rate of aquatic organism control components and has a long-lasting effect of preventing aquatic organisms from adhering to underwater materials such as fish nets.
That purpose.

[Means for solving problems]

As a result of intensive research to achieve the above object, the present inventors have discovered a fishing net barrier containing an aquatic organism control component, a resin component consisting of a hydrophilic resin and a resin compatible with this resin, and a water repellent component such as paraffin. The present invention was completed based on the discovery that the initial elution of the aquatic organism control component in a soiling agent is suppressed and the period for preventing aquatic organisms from adhering to underwater materials is extended.

The present invention contains an aquatic organism control component, a resin component consisting of a hydrophilic resin and a resin compatible with this resin, and an aqueous component, in which the water repellent component is 0.5 to 10% by weight of the total solids. %.

In the present invention, the aquatic organism control component is particularly limited as long as it is a non-metallic compound or a mixture thereof that can suppress the adhesion and reproduction of aquarium organisms such as algae, barnacles, serpura, and bryozoans to underwater materials. There isn't.

For example, nitrogen-containing organic compounds, sulfur-containing organic compounds, and nitrogen- and sulfur-containing organic compounds are known as nonmetallic compound-based aquatic organism control components, and at least one of these and tetraalkylthiuram disulfides are A mixture of these is preferably used.

More specifically, nitrogen-containing organic compounds, sulfur-containing organic compounds, nitrogen and sulfur-containing organic compounds, etc. include paratoluenesulfonamide, paratolueneethylsulfonamide, valatoluenesulfonyl chloride, methyl paratoluenesulfonate, l, 2-bis(3-methoxycarbonyl-2=thioureido)benzene, 2,4-dichloro-6-(orthochloroaniline)-3-triazine, 2゜3-dicyano-1,4-dithiaanthraquinone,
N-(trichloromethylthio)-4-cyclohexane-
Examples include 1,2-dicarboxylate, 2-(thiocyanomethylthio)benzothiazole, etc., and 2-(thiocyanomethylthio), which has extremely low toxicity and little effect on humans and fish bodies, and has high activity against aquatic organisms. ) Benzothiazole (TCMTB) is preferably used.

Tetraalkylthiuram disulfides are represented by the following general formula (1), where R is an alkyl group having 1 to 4 carbon atoms, such as tetramethylthiuram disulfisode,
Tetraethylthiuram disulfide, tetra-n-probylthiuram disulfide, etc., and tetraethylthiuram disulfide.

(TETD) is preferably used.

The blending ratio of aquatic organism control components varies depending on the combination of the above compounds, but in the case of TCMTB-TETD system, T
TETD50-200 for 100 parts by weight of CMTB
Parts by weight are preferred.

The resin component is a binder component for supporting the aquatic organism control component on underwater materials such as fish nets as a coating film,
It is a mixed resin system consisting of a hydrophilic polymer material that exhibits water-swelling properties and a polymer material that is compatible with this hydrophilic polymer material.

Examples of hydrophilic polymer substances include relatively low molecular weight acrylic resins, acrylic copolymers, polyacrylic acid and its salts, synthetic polymer substances such as polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose and its salts, hydroxypropyl cellulose, Examples include cellulose derivatives such as hydroxypropyl methylcellulose, natural polymer substances such as sodium alginate, gum arabic, and carrageenan. On the other hand, polymeric substances that are compatible with these substances vary depending on the selection of hydrophilic polymeric substances, but include water-insoluble acrylic resins, acrylic copolymers, polyacrylic acid derivatives, polyvinyl derivatives, cellulose derivatives, and hexalac. Can be mentioned.

As a resin component, a mixed resin of a relatively low molecular weight acrylic resin and/or acrylic copolymer and a relatively high molecular weight acrylic resin and/or acrylic copolymer has good compatibility and is effective in forming a coating film. It is preferably used because it has excellent properties.

The blending ratio of the resin component varies depending on the combination of the hydrophilic polymer material and the water-insoluble polymer material, but 10 to 1 part by weight of the water-insoluble polymer material is added to 100 parts by weight of the hydrophilic polymer material.
50 parts by weight is preferably employed.

The water-repellent component is a water-repellent coating film-forming substance that is incompatible with the resin component.

Examples include paraffin, silicone resin, water-repellent fluorine compounds, and paraffin is preferably used because it is inexpensive and easily available.

The fishnet antifouling agent of the present invention is a solution having a solid content of 10 to 30% by weight, in which each of the above-mentioned components is dissolved in a solvent.

The composition of each component is 20 to 20% of the aquatic organism control component in the total solid content.
70% by weight, preferably 35-50% by weight, resin content 30
~80% by weight, preferably 50-65% by weight and tn
Aqueous component 0.5-10% by weight, preferably 1-3% by weight
It is.

The organic agent is not particularly limited as long as it is a co-solvent for each of the above-mentioned components, but it is usually a single or organic agent such as toluene, xylene, solvent naphtha, butodocumene, acetone, methyl ethyl ketone, dioxane, alkyl cellosolve, chloroform, lower alcohols, etc. A mixed solvent of two or more of these is used.

In addition to the above-mentioned components, the fishnet antifouling agent of the present invention may optionally contain various additives such as colorants, plasticizers, and dialkyl polysulfisodes within a range that does not impair the effect of controlling aquatic organisms. You can.

In the present invention, the underwater material is immersed in the fish net antifouling agent and then dried to remove the solvent, thereby coating and/or impregnating the underwater material with the solid content, thereby performing antifouling treatment of the underwater material.

[For production]

As described above, the fishnet antifouling agent of the present invention is a fishnet antifouling agent consisting of an aquatic organism control component and a resin component as previously proposed by the present inventors, and further contains an IC aqueous component of 0.0% in total solid content. 5～
It is characterized in that it is added in an amount of 10% by weight.

In the drying process of underwater material treatment using the fishnet antifouling agent of the present invention, the solid content in the fishnet antifouling agent is divided into a resin component layer containing an aquarium biological control component and an F88 aqueous layer containing almost no aquatic biological control component. The layers separate into two layers, and a two-layer coating film with the ↑88 aqueous layer as the surface layer is formed on the surface of the underwater material.

As a result, the initial %J4 elution of the aquatic organism control component is suppressed, and the elution period is further extended. Therefore, aquatic organisms are prevented from adhering to the underwater material for a long period of time.

If the Iθ aqueous component in the total solid content is too small, it will not be possible to form a layer of 18 aqueous component with a thickness that can suppress the initial elution of the aquarium biological control component, and if it is too large, the 9°1Ω aqueous component The layer becomes too thick and the aquatic organism control components are not eluted. The preferred blending ratio of the T88 aqueous component is 0.5 to 10%, preferably 1 to 3%, based on the total solid content.

In addition, as mentioned above, the faa component layer with a smooth surface is
[Example] The present invention will be explained in more detail with reference to Examples and Comparative Examples.

However, the scope of the present invention is not limited in any way by the following examples.

In addition, in the following examples, "part" and "%" are based on heavy N unless otherwise specified.

(1) A mixture of 2-(thiocyanomethylthio)benzothiazole (TCMTB) and tetraethylthiuram disulfide (TETD) is used as the aquatic organism control component of the antifouling agent, and the resin component has an average molecular weight of 30°. 000 acrylic resin (
(Product name: Cohonyl, non-volatile content 45.0%, manufactured by Nippon Gosei Kagaku fi) and beaded acrylic resin with an average molecular weight of 300,000 (Product name: Dianal, BR Resin BR-95, manufactured by Mitsubishi Rayon ■). Mixed resin is used as a water repellent component, and paraffin, silicone (product name: KF-96, Shin-Etsu Chemical side type) or fluorinated metal (product name: Mo, Dayper, F-110, manufactured by NOF ■) are used. We prepared various fish net antifouling agents with different formulations.

In addition, for comparison, a fishnet antifouling agent containing no aqueous component of 1a water was prepared.

Table 1 shows the formulation of the fishnet antifouling agent.

(2) Fish v? IN treatment and ocean immersion test
A polyethylene net was immersed in the fishnet antifouling agent prepared in section 2.), and then air-dried for two days to remove the solvent, and the fishnet was antifouled.

The anti-Iη treated fishing nets and the untreated fishing nets were kept immersed 1 m below the sea surface in Ajiro Fishing Port, Shizuoka Prefecture, and the adhesion of aquatic organisms to the nets was observed and evaluated on the following three scales.

A: Adhesion of aquatic organisms is not observed.

B: Slight adhesion of aquatic organisms is observed, but it can be used as a fishing net.

C: Severe adhesion of aquatic organisms, making it unusable as a fishing net. The evaluation results are shown in Table 2.

(3) Elution test of aquatic organism control components Sample numbers ＼A-1) to (A-
3), (C-1) and (C-2) (7) Fish net antifouling agent (7 g each) was applied to 450 g of W of section 7.0, and 181 g of seawater was applied.
Using an expansion fatigue tester (manufactured by Takagi Seiki ■), shaking was applied at 100 cycles/minute, and the amount of aquatic organism control component eluted into seawater was measured.

The analysis was carried out using liquid chromatography using 500 ml of test water, which was saturated with sodium chloride, extracted with chloroform, and the analysis conditions are shown below.

Column: Finepack GELIIO Mobile phase: isooctane/methanol/ethanol = 74.5/7.
9/7.7 Mobile phase speed: 1. Oml/min Detection wavelength: 298 nm Detection sensitivity: o, osoD The total elution area for the 4 days of the elution test is shown in Table 3.

〔Effect of the invention〕

As shown in the above examples, the fish net treated with the fish net antifouling agent of the present invention maintains the effect of preventing aquatic organisms from adhering to underwater materials for a long period of 5 months in a marine immersion test ( (See Table 2).

In addition, elution test results for aquatic organism control components (see Table 3)
As shown in , a coating film formed using the fishnet antifouling agent sample (C-1) that does not contain a water-repellent component previously disclosed by the present inventors (see Comparative Example 3-1) Compared to this, the rate of elution of aquatic organism control components from the coating film formed using the fishnet antifouling agent of the present invention at the initial stage of use is significantly suppressed.

Therefore, the total elution period of the aquatic organism control component is extended, and as a result, the effect of preventing aquatic organisms from adhering to the underwater material is sustained for a long period of time.

In addition, since the initial elution of aquatic organism control components is suppressed, adverse effects on fish bodies are also eliminated.

The present invention provides a fish net antifouling agent that has a long-lasting effect on preventing aquatic organisms from adhering to underwater materials, and eliminates any adverse effects on fish bodies during the initial stage of use, and can be used with confidence. Its significance in industry, especially in the aquaculture and fisheries industry, is extremely large.

Claims (1)

[Scope of Claims] (1) Contains an aquatic organism control component, a resin component consisting of a hydrophilic resin and a resin compatible with this resin, and a water repellent component, where the water repellent component is 0.5 of the total solid content. Fish net antifouling agent (2), characterized in that the aquatic organism control component is 10% by weight, comprising 2-(thiocyanomethylthio)benzothiazole and tetraalkylthiuram disulfides ( Claim (1) wherein the fishnet antifouling agent (3) resin component described in item (1) is a mixed resin of a low molecular weight acrylic resin and a high molecular weight acrylic resin.
Fish net antifouling agent (4) The fish net antifouling agent according to claim 1, wherein the water repellent component is at least one selected from the group consisting of paraffins, silicones, and fluorine-based water repellents. stain agent